Stabilizer composition for polymer-composition melt processing and related methods

ABSTRACT

A composition having a polymer having a polymer matrix, a first stabilizer molecule within the polymer matrix, and a second stabilizer molecule within the polymer matrix, the first stabilizer molecule having the structure: 
                         
wherein each R 1 -R 4  is independently selected from the group consisting of C 1-22  alkyl, C 6-40  cycloalkyl, C 2-20  alkyl glycol ether, and Y—OH; each Y is independently selected from the group consisting of C 2-40  alkylene, C 2-40  alkylene lactone, and C 6-40  cycloalkylene; m is an integer ranging from 1 to 100; and x is an integer ranging from 1 to 1,000; the second stabilizer molecule is a monophosphite having an aryl moiety; wherein the claimed composition does not include a hindered phenolic antioxidant, lactone stabilizer, or hydroxylamine stabilizer.

CROSS-REFERENCE TO RELATED APPLICATIONS

None.

BACKGROUND OF THE INVENTION

Polymer-composition melt processing is well known and performedregularly throughout the world. There remains a need for stabilizercompositions that slow polymer degradation during melt processing.

BRIEF SUMMARY OF THE INVENTION

A composition having a polymer having a polymer matrix, a firststabilizer molecule within the polymer matrix, and a second stabilizermolecule within the polymer matrix, the first stabilizer molecule havingthe structure:

wherein each R₁-R₄ is independently selected from the group consistingof C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₂₋₂₀ alkyl glycol ether, and Y—OH;each Y is independently selected from the group consisting of C₂₋₄₀alkylene, C₂₋₄₀ alkylene lactone, and C₆₋₄₀cycloalkylene; in is aninteger ranging from 1 to 100; and x is an integer ranging from 1 to1,000; the second stabilizer molecule is a monophosphite having an arylmoiety; wherein the claimed composition does not include a hinderedphenolic antioxidant, lactone stabilizer, or hydroxylamine stabilizer.

A composition having a polymer having a polymer matrix, a firststabilizer molecule within the polymer matrix, and a second stabilizermolecule within the polymer matrix, the first stabilizer molecule havingthe structure:

wherein each R₁-R₅ is independently selected from the group consistingof C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₁₋₂₀ alkyl glycol ethers, Y₁—OH, andY₂—OH, wherein Y₁ and Y₂ are different; wherein each Y₁ and each Y₂ areindependently selected from the group consisting of C₂₋₄₀ alkylene,C₂₋₄₀ alkylene lactone, and C₆₋₄₀ cycloalkylene; n is an integerselected from the range 1 to 100; m is an integer selected from therange 1 to 100; x is an integer ranging from 1 to 1,000; and y is aninteger ranging from 1 to 1,000; the second stabilizer molecule is amonophosphite having an aryl moiety; wherein the claimed compositiondoes not include hindered phenolic antioxidants, lactone stabilizers,and hydroxylamine stabilizers.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

None.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments are directed to a composition having:

-   -   1) a polymer having a polymer matrix,    -   2) a first stabilizer molecule within the polymer matrix, and    -   3) a second stabilizer molecule within the polymer matrix.

In the embodiments, the polymer can be any known polymer. Nonlimitingexamples of useful polymers are: polycarbonate, polyamide, polyester,polystyrene, polyolefin, polypropylene, polyethylene, ethylene propyleneco-polymer, rubber, acrylonitrile butadiene styrene, butadiene rubber,polylactide, starch-based polymer, cellulose-based polymer, polyvinylchloride, polyurethane, and combinations thereof.

In a first embodiment, the first molecule and the second molecule are asfollows:

the first molecule has the structure:

wherein

-   -   each R₁-R₄ is independently selected from the group consisting        of C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₂₋₂₀ alkyl glycol ether, and        Y—OH;    -   each Y is independently selected from the group consisting of        C₂₋₄₀ alkylene, C₂₋₄₀ alkylene lactone, and C₆₋₄₀ cycloalkylene;    -   m is an integer ranging from 1 to 100; and    -   x is an integer ranging from 1 to 1,000;        and the second molecule is a monophosphite having an aryl        moiety.

Within this first embodiment, v n ay be an integer ranging from 2 to1000.

Within this first embodiment, the first molecule may have the morespecific structure:

wherein

-   -   each R₁-R₄ is independently selected from the group consisting        of C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₂₋₂₀ alkyl glycol ethers and        Y—OH;    -   each Y is independently selected from the group consisting of        C₂₋₄₀ alkylene, C₂₋₄₀ alkylene lactone, and C₆₋₄₀ cycloalkylene;        and    -   m is an integer ranging from 1 to 100; and    -   x is an integer ranging from 1 to 1,000.

Within this first embodiment, in may be 1 in the immediately abovemore-specific structure of the first molecule.

Within this first embodiment, x may be an integer ranging from 2 to 1000in the immediately above more-specific structure of the first molecule.

Within this first embodiment, the second-molecule monophosphite may havethe following structure:

wherein each R₆-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₇-C₂₃ alkyl aryl. In a morespecific example, within this first embodiment, the second-moleculemonophosphite may have the following structure:

wherein each R₈-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₇-C₂₅ alkyl aryl. In anothermore specific example, within this first embodiment, the second-moleculemonophosphite may have the following structure:

wherein each R₇-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₇-C₂₅ alkyl aryl. In stillanother more specific example, within this first embodiment, the secondmolecule may be:

-   -   i. bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, or    -   ii. 2,2,2-nitrilo[tri-ethyltris(3,3        5,5-tetra-tert-butyl-1,1-biphenyl-2,2-diyl)]phosphite.

In this first embodiment, the composition not include a hinderedphenolic antioxidant, lactone stabilizer, or hydroxylamine stabilizer.

In the first embodiment, the amount of the first molecule in thecomposition may range from 0.005 to 2.000 percent by weight of the totalcomposition, and the amount of the second molecule in the compositionmay range from 0.005 to 2.000 percent by weight of the totalcomposition. Alternatively, in the first embodiment, the amount of thefirst molecule in the composition may range from 0.005 to 1.000 percentby weight of the total composition, and the amount of the secondmolecule in the composition may range from 0.005 to 1.000 percent byweight of the total composition. Alternatively, in the first embodiment,the amount of the first molecule in the composition may be about 1percent by weight of the total composition, and the amount of the secondmolecule in the composition may be about 1 percent by weight of thetotal composition.

The first embodiment may also have an acid neutralizer within thepolymer matrix. Acid neutralizers may be divided into “inorganic”—suchas zinc oxide, synthetic hydrotalcites and Li, Na, Ca or Al (hydroxy)carbonates; and “organic”—such as salts of fatty acids or theirderivatives including calcium stearate, zinc stearate, calcium lactateand calcium stearoyl lactylate.

When employed, an acid neutralizer(s) is used in conventional amounts.In embodiments, a synthetic hydrotalcite is used in an amount rangingfrom 100 ppm to 1,000 ppm. In additional embodiments, zinc stearate isused in an amount ranging from 200 ppm to 700 ppm. In still otherembodiments, calcium stearoyl lactylate is used in an amount rangingfrom 200 ppm to 700 ppm. In still other embodiments, a combination of ahydrotalcite with an “organic” acid neutralizer can be used inconventional amounts. Persons having ordinary skill in the art will alsobe able to determine a useful amount(s) without having to exercise undueexperimentation.

The first embodiment may also have a hindered amine light stabilizer(HALS) within the polymer matrix. When employed, the HALS may be acommercially available material and may be used in a conventional mannerand amount. Persons having ordinary skill in the art will also be ableto determine a useful amount(s) without having to exercise undueexperimentation. Commercially available HALS include those sold underthe trademarks CHIMASSORB® 119; CHIMAS-SORB 944; CHIMASSORB 2020;TINUVIN® 622 and TINUVIN 770 from Ciba Specialty Chemicals Corporation,and CYASORB® UV 3346, CYASORB UV 3529, CYASORB UV 4801, and CYASORB UV4802 from Cytec Industries. In some embodiments, TINUVIN 622 ispreferred. Embodiments also include mixtures of more than one HALS.

Useful HALS include: bis (2,2,6,6-tetramethylpiperidyl)-sebacate; bis-5(1,2,2,6,6-pentamethylpiperidyl)-sebacate;n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acidbis(1,2,2,6,6,-pentamethylpiperidyl)ester; condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinicacid; condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine;tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4 butane-tetra-carbonicacid; and 1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

In a second embodiment, the first molecule and the second molecule areas follows:

-   -   the first molecule has the structure:

wherein

-   -   each R₁-R₅ is independently selected from the group consisting        of C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₁₋₂₀ alkyl glycol ethers,        Y₁—OH, and Y₂—OH;    -   wherein Y₁ and Y₂ are different;    -   wherein each Y₁ and each Y₂ are independently selected from the        group consisting of C₂₋₄₀ alkylene, C₂₋₄₀ alkylene lactone, and        C₆₋₄₀ cycloalkylene;

n is an integer selected from the range 1 to 100;

-   -   m is an integer selected from the range 1 to 100;    -   x is an integer ranging from 1 to 1,000; and    -   y is an integer ranging from 1 to 1,000;        and the second molecule is a monophosphite having an aryl        moiety.

Within this second embodiment, x may be an integer ranging from 2 to1000.

Within this second embodiment, the first molecule may have the morespecific structure:

wherein

-   -   each R₁-R₅ is independently selected from the group consisting        of C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₁₋₂₀ alkyl glycol ethers,        Y₁—OH, and Y₂—OH;    -   wherein Y₁ and Y₂ are different;    -   wherein each Y₁ and each Y₂ are independently selected from the        group consisting of C₂₋₄₀ alkylene, C₂₋₄₀ alkylene lactone, and        C₆₋₄₀ cycloalkylene;    -   n is an integer selected from the range 1 to 100;    -   m is an integer selected from the range 1 to 100;    -   x is an integer ranging from 1 to 1,000; and    -   y is an integer ranging from 1 to 1,000.

Within this second embodiment, n may be 1 in the immediately abovemore-specific structure of the first molecule. Also within the secondembodiment, m may be an integer selected from the range 2 to 100.

Within this second embodiment, x may be an integer ranging from 2 to1000.

Within this second embodiment, the second-molecule monophosphite mayhave the following structure:

wherein each R₆-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₇-C₂₅ alkyl aryl. In a morespecific example, within this second embodiment, the second-moleculemonophosphite may have the following structure:

wherein each R₈-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₇-C₂₅ alkyl aryl. In anothermore specific example, within this second embodiment, thesecond-molecule monophosphite may have the following structure:

wherein each R₇-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₂₇-C₂₅ alkyl aryl. In stillanother more specific example, within this second embodiment, the secondmolecule may be:

-   -   i. bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, or    -   ii. 2,2,2-nitrilo[tri-ethyltris(3,3        5,5-tetra-tert-butyl-1,1-biphenyl-2,2-diyl)]phosphite.

In this second embodiment, the composition may not include a hinderedphenolic antioxidant, lactone stabilizer, or hydroxylamine stabilizer.

In this second embodiment, the amount of the first molecule in thecomposition ranges from 0.005 to 2.000 percent by weight of the totalcomposition, and the amount of the second molecule in the compositionranges from 0.005 to 2.000 percent by weight of the total composition.Alternatively, in the first embodiment, the amount of the first moleculein the composition ranges from 0.005 to 1.000 percent by weight of thetotal composition, and the amount of the second molecule in thecomposition ranges from 0.005 to 1.000 percent by weight of the totalcomposition. Alternatively, in the first embodiment, the amount of thefirst molecule in the composition is about 1 percent by weight of thetotal composition, and the amount of the second molecule in thecomposition is about 1 percent by weight of the total composition.

This second embodiment may also have an acid neutralizer within thepolymer matrix. Acid neutralizers may be divided into “inorganic”—suchas zinc oxide, synthetic hydrotalcites and Li, Na, Ca or Al (hydroxy)carbonates; and “organic”—such as salts of fatty acids or theirderivatives including calcium stearate, zinc stearate, calcium lactateand calcium stearoyl lactylate.

When employed, an acid neutralize is used in conventional amounts. Inembodiments, a synthetic hydrotalcite is used in an amount ranging from100 ppm to 1,000 ppm. In additional embodiments, zinc stearate is usedin an amount ranging from 200 ppm to 700 ppm. In still otherembodiments, calcium stearoyl lactylate is used in an amount rangingfrom 200 ppm to 700 ppm. In still other embodiments, a combination of ahydrotalcite with an “organic” acid neutralizer can be used inconventional amounts. Persons having ordinary skill in the art will alsobe able to determine a useful mixings) without having to exercise undueexperimentation.

This second embodiment may also have a hindered amine light stabilizerwithin the polymer matrix. When employed, the HALS may be a commerciallyavailable material and may be used in a conventional manner and amount.Persons having ordinary skill in the art will also be able to determinea useful amount(s) without having to exercise undue experimentation.Commercially available HALS include those sold under the trademarksCHIMASSORB® 119; CHIMAS-SORB 944; CHIMASSORB 2020; TINUVIN® 622 andTINUVIN 770 from Ciba Specialty Chemicals Corporation, and CYASORB® UV3346, CYASORB UV 3529, CYASORB UV 4801, and CYASORB UV 4802 from CytecIndustries. In some embodiments, TINUVIN 622 is preferred. Embodimentsalso include mixtures of more than one HALS.

Useful HALS include: bis (2,6-tetramethylpiperidyl)-sebacate; bis-5(1,2,2,6,6-pentamethylpiperidyl)-sebacate;n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acidbis(1,2,2,6,6,-pentamethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinicacid; condensation product ofN,N-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine;tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4 butane-tetra-carbonicacid; and 1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

What is claimed is:
 1. A composition comprising: a polymer having apolymer matrix, a first stabilizer molecule within the polymer matrix,and a second stabilizer molecule within the polymer matrix, the firststabilizer molecule having the structure:

wherein each R₁-R₅ is independently selected from the group consistingof C₁₋₂₂ alkyl, C₆₋₄₀ cycloalkyl, C₁₋₂₀ alkyl glycol ethers, Y₁—OH, andY₂—OH; wherein Y₁ and Y₂ are different; wherein each Y₁ and each Y₂ areindependently selected from the group consisting of C₂₋₄₀ alkylene,C₂₋₄₀ alkylene lactone, and C₆₋₄₀ cycloalkylene; n is an integerselected from the range 1 to 100; m is an integer selected from therange 1 to 100; x is an integer ranging from 1 to 1,000; and y is aninteger ranging from 1 to 1,000; the second stabilizer molecule is amonophosphite having an aryl moiety; wherein the claimed compositiondoes not include hindered phenolic antioxidants, lactone stabilizers,and hydroxylamine stabilizers, wherein the second stabilizer moleculehas the structure:

wherein each R₆-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₇-C₂₅ alkyl aryl, andwherein the second stabilizer molecule has the structure:

wherein each R₇-R₁₁ is independently selected from the group consistingof H, C₁-C₁₀ alkyl, C₇-C₁₅ alkyl aryl, and C₇-C₂₅ alkyl aryl.